Mass treatment of cellulosic materials

ABSTRACT

This invention provides a process for deacidifying paper by contacting the paper with hydrocarbon or halocarbon solutions of certain magnesium and/or zinc alkoxyalkoxides which may have been treated with carbon dioxide to yield low viscosity solutions.

This application is a continuation of application Ser. No. 252,421,filed Sept. 30, 1988 now abandoned.

This invention concerns a method for treating cellulosic materials suchas paper by neutralizing the acidity of the paper and buffering thepaper to the alkaline side to provide protection of the paper frompost-treatment acid attack and to improve paper performance and novelchemical compositions useful in practicing this method of papertreatment.

Paper has been made for nearly 2,000 years; some early papers havelasted half of this time and others made during the middle ages are inexcellent condition. Ancient handmade paper was too soft a material forreceiving ink so it was sized by dipping the sheets in hot animalgelatin or starch. As papermakers shifted to machine made paper,different procedures for sizing the paper were necessary. This problemwas solved by "tub sizing," which is done by adding a mixture of alumand rosin to the wet fiber slurry before the sheet was formed on themachine, thereby coating the fibers in the paper with rosin and makingthe paper suitable for use in printing paper or writing paper.Unfortunately, alum, aluminum sulfate [Al₂ (SO₄)₃ ], which is used intub sizing to uniformly distribute the rosin throughout the sheet is oneof the major causes of acid in paper. Subsequent reaction betweenaluminum sulfate and water produces sulfuric acid. Other sources of acidin the paper, of course, include industrial atmospheres that have sulfurdioxide and nitrogen oxides in the air which form acid in the paper.Thus, most books printed in the last 100 or 150 years were printed onacid paper which becomes brittle and disintegrates in a period of 5-75years or more depending on the care with which books have been stored.

Almost every library in the world is filled with books made with thisacid paper, and therefore, have large collections of books which aredisintegrating. This problem of acidity in books has been recognized forquite a long time and a great deal of work has been done to establish aprocess for deacidifying such books. A recent report, "MassDeacidification for Libraries" by George Martin Cunha, Adjunct Professorof Conservation, College of Library and Information Science, Universityof Kentucky, was printed in Library Technology Reports, Volume 23, No.3, May-June 1987. The Cunha report claims to have reviewed all knownexperiments with methods of mass deacidification and six were thoroughlyinvestigated. One of the major methods of mass deacidificationconsidered was the so-called diethyl zinc (DEZ) system which appears tobe covered by U.S. Pat. Nos. 3,969,459 and 4,051,276 assigned to theUnited States of America as represented by the Librarian of Congress.Mass deacidification with diethyl zinc is a 50-55 hour three-phaseprocess consisting of preconditioning, permeation and passivation. TheDEZ system under development by the Library of Congress will handlethousands of books per cycle. However, liquid diethyl zinc is pyrophoric(will spontaneously ignite when exposed to air) and will reactexplosively with water. The fire and explosive hazards of diethyl zincmake it a dangerous chemical to work with and probably one that everylibrary could not contemplate using. Moreover, the fire and explosivehazards have caused considerable expensive design problems in developingsuitable equipment for this process.

Another major method of mass deacidification evaluated in the Cunhareport was one employing methoxymagnesium methylcarbonate in a solutionof alcohol and fluorocarbons in treating books in mass. The system is aliquid process designed to dissolve, transport and deposit the chemicalsinto book pages to neutralize acids present in the paper and to depositbuffering chemicals that will neutralize any acids that may subsequentlycontaminate the paper. This system appears to be covered by U.S. Pat.No. 4,318,963 of Richard D. Smith and U.S. Pat. No. 3,939,091 of GeorgeB. Kelly (assigned to the United States of America as represented by theLibrarian of Congress) and is based on earlier U.S. Pat. Nos. 3,676,055and 3,676,182 to Richard D. Smith. The process employsmethoxymagnesiummethyl carbonate dissolved in a liquid solution offluorocarbons and methyl alcohol. This alcohol is necessary to promotesolution of the magnesium compound. This solution reacts with water inthe paper to form magnesium carbonate, magnesium hydroxide and magnesiumoxide, some of which react with the acid in the paper to formneutralized salts. The remaining mixture of carbonate, hydroxide andoxide remains in the paper as basic magnesium carbonate which forms analkaline reserve or buffering agent that will neutralize future acidcontamination of the paper. Disadvantages of the process includefeathering of alcohol-soluble inks and colors and attack on some highlynitrated book covers, and thus a pre-sorting by uses is required.

According to the Cunha report, ammonia has been used in India for massdeacidification of books. Langwell in England used cyclohexylaminecarbonate, while in the United States the Barrow Laboratory in Virginiaconceived ceived the use of morpholine (U.S. Pat. No. 3,771,958). Themorpholine, ammonia and cyclohexylamine carbonate systems weremoderately effective deacidifiers, but did not provide a buffer in thepaper to provide protection of the paper from acid attack. A patent toR. A. Kundrot (U.S. Pat. No. 4,522,843) claims a method of deacidifyingbooks usrng alkaline particles of a basic metal suspended in an aerosol.

The present invention provides a process in which certain carbonatedmagnesium alkoxyalkoxides can be readily prepared and dissolved in awide variety of solvents both liquid and gaseous at ordinarytemperatures and said solutions applied to paper, books, and othercellulosic materials to both deacidify, coat them in a protectivemanner, and to provide them with added strength.

SUMMARY OF THE INVENTION

In accordance with this invention, there is provided a process fordeacidifying paper using certain magnesium and zinc alkoxyalkoxides,described in U.S. Pat. No. 4,634,786, cols. 7-10 and 17, and dissolvedin hydrocarbon or halocarbon solvents, which are treated with gaseouscarbon dioxide to, unexpectedly, yield solutions possessing a muchreduced viscosity. These solutions can be readily solvent-stripped toyield fluid, somewhat viscous liquid residues, which readily redissolvein a variety of gaseous and liquid hydrocarbon and halocarbon solventsto yield highly concentrated, low viscosity solutions, which can beadjusted in concentration to that needed for treatment of books andpaper. Optionally an aluminum or zinc alkoxide can be added to thesecarbonated alkoxide compositions to help solubilize the components ofthe compositions.

Examination of the resulting carbonated magnesium-containing residues,or solutions thereof, show that approximately 50% of the magnesiumalkoxyalkoxide groupings have been converted to magnesium alkoxyalkylcarbonate groupings.

These carbonated magnesium alkoxyalkoxides (or magnesium alkoxyalkylcarbonates) either in a neat form or in a solution form, can be treatedwith gases, such as gaseous hydrocarbons, for example ethane or carbondioxide, under relatively low pressure, to yield greatly expandedsolutions of the magnesium-containing product. Thus, for example,treatment of a 5-10 weight percent solution of magnesiumn-hexylcarbitolate (carbonated) in hexane with sufficient ethane gas toraise the pressure to about 500 psi causes the liquid volume of thesolution to increase to approximately twice its original volume.

The above property of volume expandability can be utilized toalternately cover and uncover paper products suspended in the samechamber. Thus, a strip of paper cut from a book, when suspendedvertically above the original carbonated magnesium n-hexylcarbitolatesolution in hexane, is contacted by the solution to a point more thanhalfway to the top of the paper strip, by pressurizing themagnesium-containing solution with ethane as described above. Release ofthe pressure and venting of the gas returns the liquid solution to itsoriginal volume below the bottom edge of the paper strip.

Said paper strip is now treated evenly with the magnesium-containingcompound and possesses a satiny feel.

Unlike magnesium alkoxide carbonates described in the literature, suchas methoxymagnesium methyl carbonate no alcohol co-solvent is requiredto maintain the solubility of the carbonated magnesium alkoxides of thisinvention either in hydrocarbon or halocarbon solution. Alcoholco-solvents have been shown to be detrimental in book deacidification,dissolving inks and colors and attacking plastic covers in the books.

In addition, other metallic alkoxides (such as aluminum alkoxides) basedon alcohols described in U.S. Pat. No. 4,634,786, cols. 7-10, and 17 canbe prepared in liquid form and dissolved in a variety of solvents,including hydrocarbons and halocarbons. The corresponding aluminumalkoxides can be readily prepared and combined with the carbonatedmagnesium and/or zinc alkoxides of this invention and dissolved in avariety of solvents to yield solutions which can be gas expanded or useddirectly in the treatment of paper and books.

Thus, it is one advantage of this invention to make available carbonatedmagnesium alkoxides possessing a high solubility in liquid hydrocarbonand halocarbon solvents, said solutions also having the property of lowviscosity.

It is another advantage of this invention to provide a process forgreatly expanding the volume of these solutions of carbonated magnesiumalkoxides without causing the separation of carbonated magnesiumalkoxides from these solutions.

It is another advantage of this invention to provide a simplifiedprocess for the utilization of such expanded solutions of carbonatedmagnesium alkoxide in the treatment of paper, books, and othercellulosic materials, whereby the latter are deacidified, buffered, andgiven a permanent finish by these expanded solutions.

It is another advantage of this invention to provide a simplifiedprocess for the utilization of solutions of carbonated magnesiumalkoxide, per se, in the treatment of paper, books, and other cellulosicmaterials whereby the latter are deacidified, buffered and strengthenedby these solutions.

It is yet another advantage of this invention to provide suchdeacidifying carbonated magnesium alkoxide solutions in the essentialabsence of co-solvent alcohols.

It is also an advantage of this invention to provide other low viscositymetallic alkoxides solutions for use as deacidifying solutions in liquidor gaseous hydrocarbon and halocarbon solvents, such as, for examplealuminum alkoxides, alone or in combination with the carbonatedmagnesium and zinc alkoxides of this invention.

Detailed Description of the Invention

A process for deacidifying paper, books and other cellulosic materials,according to this invention comprising contacting the cellulosicmaterials with an effective amount of a compound of the formula

    X.sub.y M.sup.a (OR).sub.a-y.(R.sup.1 OH).sub.x            ( 1)

wherein:

(I) --OR is a group selected from 2-alkoxyalkoxy- andω-alkoxypoly(alkoxy) groups of the formula [--OCH(R²)CH₂ --OCH(R²)CH₂--_(n) OR³ ] wherein R² is selected from H and --CH₃ and R³ is selectedfrom alkyl groups of 1 to 20 carbon atoms, cycloalkyl groups of 3 to 20carbon atoms and aryl, arylalkyl and alkylaryl groups of 6 to 20 carbonatoms and n is a value of zero to 100;

(II) X-- is a group selected from

(a) alkoxy groups of the formula --OR⁴ wherein R⁴ is selected from alkylgroups containing 1 to 20 carbon atoms, cycloalkyl groups containing 3to 20 carbon atoms and aryl, arylalkyl and alkylaryl groups containing 6to 20 carbon atoms;

2-alkoxyalkoxy- and ω-alkoxypoly(alkoxy) groups of the formula

    [--OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2)CH.sub.2 --.sub.n OR.sup.3 ](2)

wherein R², R³ and n have the hereintobefore ascribed meanings;

(c) 2-dialkylaminoalkoxy- and ω-dialkylaminopolyalkoxy groups of theformula

    [--OCH(R.sup.2)CH.sub.2 --OCH(R.sub.2)CH.sub.2 --.sub.n NR.sup.3.sub.2 ](3)

wherein R₂, R³ and n have the hereintobefore ascribed meanings;

(d) halogen selected from chlorine and bromine;

(e) alkylcarbonato groups of the formula [--OC(O)OR⁴ ] wherein R⁴ hasthe hereintobefore ascrib mean and may also be 2-alkyoxyalkoxy- andω-alkoxypolyalkoxy groups of the formula

    [--OCH(R.sup.2)CH--OCH(R.sup.2)CH.sub.2 --.sub.n OR.sup.3 ](4)

wherein R², R³ and n have the hereintobefore ascribed meanings;

(f) an organic group --R⁴ wherein R⁴ has the hereintobefore ascribedmeaning;

(g) an acyloxy group of the formula [--(O)CR⁴ ] wherein R⁴ has thehereintobefore ascribed meaning;

(III) M is a metal selected from groups IIa and IIb of the periodictable and aluminum and mixtures thereof;

(IV) R¹ OH is a compound in which RIO is a group selected from

(h) alkoxy groups of the formula R⁴⁰ wherein R⁴ has the hereintobeforeascribed meanings;

(i) 2-alkoxyalkoxy- and ω-alkoxypoly(alkoxy) groups of the formula[--OCH(R²)CH₂ --OCH(R²)CH_(2-n) OR³ ] wherein R², R³ and n have thehereintobefore ascribed meanings;

(j) 2-dialkylaminoalkoxy- and ω-dialkylaminopoly(alkoxy) groups of theformula [--OCH(R²)CH₂ --OCH(R²)CH_(2-n) NR³ ₂ ] wherein R², R³ and nhave the hereintobefore ascribed meanings;

(V) a is the valence of the metal M;

(VI) y has a value between zero and one; and

(VII) x has a value of zero to two.

Examples of compounds of the formula

    X.sub.y M.sup.1 (OR).sub.a-y.(R.sup.1 OH).sub.x

include but are not limited to

    __________________________________________________________________________    (a)                                                                             CH.sub.3 OMgOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5            C.sub.6 H.sub.13 OMgOCH(CH.sub.3)CH.sub.2 --OCH(CH.sub.3)CH.sub.2             OCH.sub.3                                                                     C.sub.2 H.sub.5 OZnOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --) .sub.6.4        OCH.sub.3.(C.sub.4 H.sub.9 O--(CH.sub.2 CH.sub.2 O--) .sub.3H).sub.0.5        C.sub.3 H.sub.7 OAL(OCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --) .sub.2OC.      sub.4 H.sub.9).sub.2                                                        (b)                                                                             CH.sub.3 O(CH.sub.2 CH(CH.sub.3)O--) CH.sub.2 CH(CH.sub.3)OMgOCH.sub.2        CH.sub.2 --(OCH.sub.2 CH.sub.2).sub.3 OCH.sub.3                               C.sub.4 H.sub.9 O(CH.sub.2 CH.sub.2 O).sub.2 --CH.sub.2 CH.sub.2              OZnO--CH(CH.sub.3)CH.sub.2 OCH--(CH.sub.3)CH.sub.2 OCH.sub.3.(C.sub.2         H.sub.5 OH)                                                                   C.sub.2 H.sub.5 OCH.sub.2 CH.sub.2 OAl(OCH.sub.2 CH.sub.2 OCH.sub.2           CH.sub.2 OC.sub.4 H.sub.9).sub.2                                            (c)                                                                             (CH.sub.3).sub.2 N--CH.sub.2 CH.sub.2 OMgOCH.sub.2 CH.sub.2 OCH.sub.2         CH.sub.2 OC.sub.2 H.sub.5.C.sub.2 H.sub.5 OH                                  (C.sub.2 H.sub.5).sub.2 NCH.sub.2 CH(CH.sub.3)OZnOCH.sub.2 CH.sub.2           (OCH.sub.2 CH.sub.2 --) .sub.6.4 OCH.sub.3.(C.sub.2 H.sub.5)NCH.sub.2         CH(CH.sub.3)OH                                                                (CH.sub.3).sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OAl(OCH(CH.sub.3)      CH.sub.2 (OCH--(CH.sub.3)CH.sub.2 --) .sub.2OCH.sub.3                       (d)                                                                             ClMgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.3 OC.sub.4 H.sub.9.C.sub      .4 H.sub.9 O(CH.sub.2 CH.sub.2 O--) .sub.3H                                   BrZnOCH(CH.sub.3)CH.sub.2 OCH(CH.sub.3)CH.sub.2 OCH.sub.3                     ClAlOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --) .sub.2OC.sub.4 H.sub.9       (e)                                                                             C.sub.2 H.sub.5 OC(O)OMgOCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.4         H.sub.9                                                                       CH.sub.3 OC(O)OZnOCH(CH.sub.3)CH.sub.2 --O--CH(CH.sub.3)CH.sub.2              OCH.sub.3..sub.0.5 --(C.sub.4 H.sub.9 O(CH.sub.2 CH.sub.2 O).sub.3 H)         CH.sub.3 OC(O)OMgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 -- ) .sub.2OC.su      b.2 H.sub.5..sub.0.5 --C.sub.4 H.sub.9 O(CH.sub.2 CH.sub.2 O--)               .sub.3H                                                                     (f)                                                                             C.sub.4 H.sub.9 MgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --) .sub.6.4         OCH.sub.3                                                                     C.sub.2 H.sub.5 ZnOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --) .sub.6.4         OCH.sub.3                                                                     C.sub.6 H.sub.5 Al(OCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.2              OC.sub.4 H.sub.9).sub.2                                                     (g)                                                                             CH.sub.3 CH.sub.2 C(O)OMgOCH(CH.sub.3)CH.sub.2 OCH(CH.sub.3)CH.sub.2          OCH.sub.3.C.sub.2 H.sub.5 OH                                                  C.sub.4 H.sub.9 C(O)OZnOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --)             .sub.6.4 OCH.sub.3                                                            C.sub.4 H.sub.9 C(O)OAlOCH(CH.sub.3)CH.sub.2 OCH(CH.sub.3)CH.sub.2            OCH.sub.3                                                                   __________________________________________________________________________

Substituted alkoxides, such as zinc or magnesium alkoxides of the aboveformula (1), wherein II is (a) or (b), dissolved in hydrocarbon orhalocarbon solvents are treated, according to this invention, withgaseous carbon dioxide at atmospheric pressure and above, to convertthem to carbonated magnesium or zinc alkoxides, (II) (e) above) asdescribed in U.S. Pat. No. 3,939,091, col. 3, which discloses passingcarbon dioxide into a solution of magnesium methoxide (8 to 9 weightpercent) in methanol until the solution or suspension is saturated withcarbon dioxide.

Carbonation of the magnesium or zinc alkoxide solutions can be done attemperatures between about 0° and about 100° C. and at pressures betweenabout atmospheric and 1000 psi. Then solvents are stripped from thesolution under reduced pressure to yield the neat liquid carbonatedmagnesium or zinc alkoxides (or alkoxymetalalkoxyalkyl carbonates) shownbelow. Small amounts (up to 2 moles per mole of carbonated metalalkoxide) of alcohols may be present which are complexed (tightly held)with the carbonated metal alkoxide and are beneficial in promotingsolubilization of the carbonated metal alkoxide in the solvents used fortreatment of the cellulosic materials.

Examples of the metal alkoxides which can be carbonated with carbondioxide according to this invention are magnesium and zincbis-2-alkoxyalkoxides and magnesium and zincbis-omega(ω)-alkoxypolyalkoxides having the general formula

    R.sup.4 O(CH.sub.2 CH(R.sup.2)O).sub.n CH.sub.2 CH(R.sup.2)O).sub.y M(OCH(R.sup.2)CH.sub.2 (OCH(R.sup.2)CH.sub.2).sub.m OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 5)

wherein M is selected from m;agnesium, zinc and mixtures thereof, R³ andR⁴ are independently selected from C₁ to C₁₈ hydrocarbyl groups, Rl isselected from C₁ to C₁₈ hydrocarbyl groups and a R³ O (CH₂ CH(R²)O--_(n)CH₂ CH(R² -- group, n and m are values from 1 to 20,R² is selected fromhydrogen and methyl, y is a value from 0.01 to 1.0 and x is a value fromzero to two.

The resulting carbonated products have carbon dioxide (CO₂) incorporatedinto only one side of the metal alkoxide resulting in a CO₂ /Mg ratio ofabout one, and possessing one of the following two structures:

    (R.sup.4 O(CH.sub.2 CH(R.sup.2 O).sub.n CH.sub.2 CH(R.sup.2)O).sub.y M(OC(O)OCH(R.sup.2)CH.sub.2 (OCH(R.sup.2 (CH.sub.2).sub.m OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 6)

    and

    (R.sup.4 O(CH.sub.2 CH(R.sup.2)O).sub.n CH.sub.2 CH(R.sup.2)OC(O)O).sub.y M(OCH(R.sup.2 CH.sub.2 (OCH(R.sup.2)CH.sub.2).sub.m OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 7)

wherein M is selected from magnesium, zinc and mixtures thereof, n and mare values from 1 to 18, R² is hydrogen or methyl, R³ and R⁴ areindependently selected from C₁ to C₁₈ hydrocarbyl groups, R¹ is selectedfrom C₁ to C₁₈ hydrocarbyl groups and a R³ O(CH₂ CH(R²)O--_(n) CH₂ CH(R²-- group wherein R³ selected from C₁ to C₁₈ hydocarbyl groups, y is avalue from 0.01 to 1.0 and x is a value from between zero and two and asolvating amount of a solvent selected from aromatic hydrocarbons,halocarbons and mixtures thereof. Examples of these carbonated alkoxidesare shown in Table 1.

Other magnesium and zinc alkoxides, which are a mixture of the typesshown above with aliphatic or cycloaliphatic C₁ to C18 metal alkoxidesmay also be half-carbonated to yield novel products of this invention.These metal alkoxides have the general formula:

    (R.sup.4 O).sub.y M(OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2)CHhd 2).sub.n OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 8)

wherein M is selected from magnesium, zinc and mixtures thereof, R³ andR⁴ are independently selected from C₁ to C₁₈ hydrocarbyl groups, R¹ isselected from C₁ to C₁₈ hydrocarbyl groups and R³ O(CH₂ CH(R²)O--_(n)CH₂ CH(R²)--, n is value from 1 to 20, R² is selected from hydrogen andmethyl, y is a value from 0.01 to 1.0 and x is a value from zero to two.

The resulting carbonated products possess one of the two followingstructures:

    (R.sup.4 O).sub.y M(OC(O)OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2 CH.sub.2--n OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 9)

    and

    (R.sup.4 O(O)CO).sub.y M(OCH(R.sub.2)CH.sub.2 --OCH(R.sup.2)CH.sub.2--n OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                      ( 10)

wherein M is selected from magnesium, zinc, and mixtures thereof, n is avalue from 1 to 20, y is a value from 0.01 to 1, R³ and R⁴ areindependently selected from C₁ to C₁₈ hydrocarbyl groups, R₂ is selectedfrom hydrogen and methyl, R¹ is selected from hydrocarbyl groups havingone to eighteen carbon atoms anda R³⁰ (CH₂ CH(R²)O--_(n) CH₂ Ch(R² --group wherein R³ is a C₁ to C₁₈ hydrocarbyl group, R² is selected fromhydrogen and methyl, x is a value from zero to two and a solvatingamount of a solvent selected from aromatic hydrocarbons, halocarbons andmixtures thereof. Examples of these carbonated metal alkoxides are shownin Table 2.

Aluminum and zinc alkoxides can be added to these carbonatedcompositions and to the other carbonated compositions of this inventionto help solubilize the components of the compositions.

The products of the invention may be prepared via a number oftechniques, known to the art, such as by reacting a suspension ofmagnesium metal, or magnesium amide or C₁ -C₃ magnesium dialkoxides in ahydrocarbon or halocarbon so . or by reacting a solution of adialkylmagnesium or a dialkylzinc compound in a hydrocarbon solvent,with a 2-alkoxy-substituted alkanol (ROCH₂ CHR'OH) wherein R is a C₁-C₁₂ hydrocarbyl and R' is hydrogen or methyl; or a mem oftthe group ofω=alkoxy-poly(alkoxy)alkanols, of the formula RO(CH₂ CH()R')O)_(n) CH₁CH(R')OH wherein R is a C₁ -C₁₈ hydrocarbyl group, R' is a methyl groupor hydrogen, and n is from 1 to about 100, and carbonating the productsthereof.

The 2-alkoxyalkanols (ROCH₂ CHR'OH) where R is hydrogen, also have thetrade name Cellosolves (Union Carbide) and are exemplified by thesubstances Methyl Cellosolve.SM. (CH₃ OCH₂ CH₂ OH), Butyl Cellosolve™(C₄ H₉ OCH₂ CH₂ OH) and Hexyl Cellosolve (C₆ H₁₃ OCH₂ CH₂ OH).

The ω-alkoxypoly(alkoxy)alkanols, of the formula (RO(CH₂ CH(R)O)_(n) CH₂CH(R')OH), where n is one and R' is hydrogen, also have the trade nameCarbitol and are exemplified by the substances Methyl Carbitol, ButylCarbitol and Hexyl Carbitol. Higher n numbers, e.g. where n is 2, giveMethoxy, Ethoxy, and Butoxytriglycol, and where n is 6 or more, MethoxyPolyethylene Glycols (trademark Carbowax MPEG, Union Carbide).

These can be used in mixtures thereof with each other or with C₁ to C₁₂alcohols selected from the group of (a) aliphatic 2-alkyl-substituted C₄-C₁₂ primary monohydric alcohols; or (b) aliphatic C₃ -C₁₂ secondary ortertiary alcohols; or (c) aliphatic C₁ -C₁₂ primary linear unsubstitutedalcohols; and removing hydrogen or ammonia which forms during thereaction.

The starting magnesium or zinc alkoxide may also be prepared by reactinga solid magnesium or zinc dialkoxide of the formula Mg(OR)₂ or Zn(OR)₂in which R is a C₁ -C₁₂ hydrocarbyl group, with at least two molar equiof a 2-alkoxy-substituted alkanol, ROCH₂ CHR'OH, or anω-alkoxypoly(alkoxy)alkanol, RO(CH₂ CH(R')O)OH wherein R is a C₁ -C₁₂hydrocarbyl group and R' is hydrogen or a methyl and n is from 0 toabout 100, isolating the resultant mobile liquid product, and dissolvingsame in a hydrocarbon or chlorinated hydrocarbon or halocarbon solventof choice, or by reacting a solid magnesium dialkoxide with just onemolar equivalent of a 2-alkoxyalkanol or ω-alkoxypoly(alkoxy)alkanol ina hydrocarbon or halocarbon solvent, or by reacting dialkylmagnesium ordialkylzinc compounds of the formula MgR₂ or ZnR₂ in which R is a C₁-C₁₂ hydrocarbyl group, with at least two molar equivalents of a2-alkoxy-substituted alkanol, ROCH₂ CHR'OH, orω-alkoxypoly(alkoxy)alkanol or mixtures of such alkanols, in which R isa C₁ -C₁₂ hydrocarbyl group and R' is hydrogen or a methyl group, sometypical examples of which are as described in U.S. Pat. No. 4,634,786,incorporated herein by reference, and then carbonating the productthereof.

After carbonation is complete, as evidenced by no further evolution ofheat, the resulting liquid products and solutions thereof of themagnesium or zinc alkoxide carbonates are unexpectedly more fluid (lessviscous) than the original magnesium or zinc alkoxide products andsolutions before carbonation, especially in the case of the higherhomologs where n is greater than one; this is evident even aftercomplete removal of solvents. For example, a sample of magnesiumbutoxytriglycolate (n=2) in heptane (before carbonation) was stripped ofsolvent and found to be so extremely viscous that the product would notflow. Even after addition of 20 weight percent of hexane, the productwas still not fluid enough to pour. On the other hand, another sample ofthe same magnesium butoxytriglycolate, after carbonation and stripping,yielded a completely fluid, low viscosity liquid residue, which wasreadily pourable and which formed fluid pourable solutions in hexane atall concentrations. (Similar results are evident when zin is used inplace of magnesium.)

Comparison of this thinning effect on carbonation of the magnesiumalkoxides of this invention with the result obtained on carbonation ofother hydrocarbon-soluble alkoxide types described in U.S. Pat. No.4,634,786 (magnesium 2-alkyl-substituted alkoxides) hydrocarbon solubleiu alkoxide complexes described in U.S. Pat. Nos. 4,246,383, 4,426,316,and 4,244,838 is striking. Treatment of a 0.6M solution of magnesium2-methylpentyloxide solution in heptane with carbon dioxide, resulted ina solid gel while a much lower concentration of the same compound gave aprecipitate rather than a solution on carbonation. In another case, asample of a 1:1 complex of magnesium and aluminum ω-butoxides dissolvedin heptane/hexane was carbonated resulting in gelation of the solution.Neither gelation nor precipitation leads to a useful product for thepurpose of evenly treating cellulosic materials. Alcoholic co-solventswhich might aid in dissolving these products are not desirable for thepurpose of deacidifying paper and books, as was mentioned earlier.

The carbonated magnesium or zinc alkoxides of this invention possess theproperty of essentially complete miscibility in a variety of normallyliquid hydrocarbon solvents such as, for example, pentane, hexane,heptane, benzene, toluene, and cyclohexane as well as gaseoushydrocarbons such as ethane, propane, propylene and butanes. Inaddition, said carbonated magnesium or zinc alkoxides are soluble innormally liquid halocarbons, such as 1,1,2-trichlorotrifluoroethane,symmetrical tetrachlorodifluoroethane, perchlorethylene, chloroform andmethylchloroform and mixtures thereof. Other gaseous halocarbonscontemplated as solvents are chlorotrifluoromethane,chlorodifluoroethane and 1,2-dichlorotetrafluoroethane.

Another property inherent in the carbonated magnesium or zinc alkoxidesof this invention is the great expandability of their volumes eitheralone or in solution on treatment with certain gases such as, forexample, the hydrocarbon gases ethane, propane, and butane, or thechlorofluorocarbon or fluorocarbon gases such as fluoroform,hexafluoroethane, tetrafluoroethane, perfluoropropane,chlorotrifluoroethane, chlorodifluoroethane and1,2-dichlorotetrafluoroethane and even gases such as carbon dioxide.This property of solution expandability was found to be useful in thetreatment of cellulosic materials such as paper and books. Althoughsolution expandability on gasification is not a new concept, it has beennoted that such solution expansion must be controlled by judiciouspressure regulation so as not to exceed the solubility of the magnesiumor zinc compound in the combination of gaseous and liquid solvents.Beyond a certain pressure precipitation of the dissolved magnesium orzinc compounds occurs, leading to a non-homogeneous deposition of adeacidifying agent on the books. For example, ethane gas reproduciblygave expanded solutions of the magnesium or zinc compounds of thisinvention to at least twice their original volume under pressures of 500psi or less without thickening or precipitation of the solutions. Inaddition, the original volume of ungasified solution could be reversiblygenerated by venting of the dissolved ethane gas. It is important tonote that precipitation of the magnesium compounds of this invention canbe made to occur using ethane by raising the pressure above about 500psi (pressure depends upon the concentration of magnesium in theoriginal solution and its solvent composition), but is undesirable forthe purpose of treatment of cellulosic materials, leading to streaky,sticky finishes.

Similarly, carbon dioxide gas expands perchloroethylene solutions of thecarbonated magnesium or zinc alkoxides to over twice their originalvolume at pressures not much above 650 psi.

Thus, this property of expandability of hydrocarbon and halocarbonsolutions of the magnesium or zinc compounds of this invention was foundto be applicable to the treatment of cellulosic materials such as paperand books, by the simple expedient of suspending the cellulosicmaterials just above the level of the liquid hydrocarbon solutions ofthe magnesium or zinc compounds, pressurizing the hydrocarbon orhalocarbon solutions with ethane or carbon dioxide gas to an internalpressure of about 500 psi (650 psi for CO₂), so as to cause the originalsolution volume to expand sufficiently (at least double) to cover thesaid cellulosic material, and, after a sufficiently long treatment time,to vent the dissolved ethane or carbon dioxide gas, thus reducing thevolume of the hydrocarbon (or halocarbon) solution to its originalvolume and below the level of the treated cellulosic material. Onremoval from the pressure chamber, the treated cellulosic material wasfound to be dry and possessed a satiny smooth finish. Any number ofconsecutive treatments of the cellulosic material for varying lengths oftime as described above can be carried out so as to impart the desiredprotective finish to the cellulosic material simply by alternativelyexpanding and contracting the hydrocarbon or halocarbon solution. Thus,for example, although single pieces of paper receive a deacidifyingfinish with as little as one such expansion/contraction cycle for asshort a contact time as 15 seconds, multiple pieces of paper such asbook pages may require several such cycles with longer contact timeperiods.

Generally, a pressure range for the carbonated magnesium alkoxidesolution "expanding" gas should be from about 100 psi to about 1000 psi.Supercritical gas pressure or temperatures are not required. Inaddition, elevated temperatures above ambient ar not required during theexpansion/contraction phases of the treatment of cellulosic materials.

It is also possible to use the hydrocarbon or halocarbon solutions ofthe carbonated zinc and magnesium alkoxides directly as deacidifyingmedia, that is, without gaseous expansion. Thus, an approximately 8volume/volume % (v/v%) solution of magnesium butoxytriglycolate (MBTG)in Freon TF (1,1,2-trichlorotrifluoroethane) was used to treat pagestaken from a book, under various conditions, and found to evenlypenetrate the pages, leaving about a 2% residual buffer of magnesium,calculated as MgCO₃. Strengthening of the pages was shown by an increasein the number of folds required to break a page in half (parallel to thebinding) in the treated vs. the untreated samples, of about 400%. Othersolvents may also be used, as mentioned above.

The concentration of the metal ion in the deacidifying treatment mediummay be varied widely, but generally will lie in the range of 0.01 to 1.0molar. More preferably, the range of metal ion concentration will lie inthe range of 0.02 to 0.5 molar and, most preferably, 0.05 to 0.25 molar.Sufficient metal ion, calculated as MgCO₃, is generally desirable toprovide about 2% MgCO₃ as both deacidifying agent and residual buffer,although this value may not be as critical where additionalstrengthening of the cellulosic material is being provided as by theproducts of this invention.

Naturally, the effects of time of treatment (treatment cycle) and numberof treatment cycles is an important consideration and will also affectthe metal ion concentration being deposited. Thus, in certain singlepage treatments, although about 2-5 minutes sufficed to give pagescontaining 2% of MgCO₃ (equivalent), a 10 minute treatment time gavepages with the most even distribution of MgCO₃.

Another factor controlling metal ion deposition which needs to beempirically determined in each case is the type of cellulosic materialbeing treated, which material can vary widely in composition.

As mentioned earlier for the gaseous expansion process, temperature andpressure will also play a role in metal ion deposition, and it isexpected that higher values of both will promote (increase) metal ionconcentrations in the treated products.

For such treatments, generally short cycles are preferable, of the theorder of an hour or so or less, depending on the number and thickness ofthe items being treated, and on the porosity of the cellulosic materialthe items are made from. Thus, a 3 inch by 3 inch by 1 inch thick bookcontaining porous paper was uniformly treated in 10 minutes, with a pagetaken from the center of the book showing the presence of about 1.5%MgCO₃.

It is believed that the magnesium and zinc compounds of this inventionpossess a unique chemical structure which can readily complex(associate) with the many hydroxyl groupings in cellulosic materials,thus binding the magnesium or zinc compounds tightly to the cellulosicmaterials and providing the latter with an additional (todeacidification) protective film or coating. As the number of ethoxy orpropoxy units in the magnesium or zinc compounds increases, it has beenfound that the film or coating provided will also impart a strengtheningproperty to the cellulosic material.

Thus, for example, the number of folds before breakage of pages takenfrom an old book which had been previously treated with the followingmagnesium alkoxide carbonates in a Freon TF Solution increased as shown:

    ______________________________________                                        as the                                                                        Magnesium Alkoxide (Carbonate)                                                                   No. of folds to break                                      ______________________________________                                        Magnesium Butoxytriglycolate                                                                     29                                                         Magnesium Butoxytriglycolate/                                                                    35                                                         Methoxypolyethoxide.sup.(a)                                                   Magnesium Bis-Methoxypoly-                                                                       59                                                         ethoxide                                                                      None                5                                                         Magnesium Methoxide                                                                               4                                                         ______________________________________                                         .sup.(a) number of ethoxy units is an average of 7.4.                    

In contrast to previously utilized carbonated magnesium alkoxides (suchas methoxymagnesium methyl carbonate) treatments where no strengtheningeffect is noted, not only do the magnesium salts of this inventionadhere to the cellulosic structure of the paper, but the by-products ofthe deacidification process, the ω-alkoxy(poly)ethoxy andω-alkoxy(poly)propoxy alcohols themselves, also do so. Thus, there is nomassive venting of volatile alcohols, such as methanol, from the pagesof a book during the continuing deacidification processes that may occuron library bookshelves in a book with the passage of time.

Metallic alkoxides of the type shown above for magnesium and zinc, butwithout carbonation, can also be used in such treatments, either alone,or in admixture with the carbonated magnesium and zinc alkoxides. Thus,for example, aluminum alkoxyalkoxides and ω-alkoxypolyalkoxides can beprepared in pure form and used alone or in admixture with the carbonatedmagnesium and zinc alkoxyalkoxides and alkoxypolyalkoxides describedabove. Typical aluminum alkoxides of this type are aluminumtris-hexylcarbitolate, aluminum tris-ω-methoxypolyethoxide,ethoxyaluminum bis-ω-methoxypolyethoxide, and the like.

Other partially alkoxylated alkylmetallic compounds may also be used insolution form to treat cellulosic materials. These alkylmetallicalkoxides have the generic formula:

    (R.sup.1).sub.y M.sup.a (OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2)Ch.sub.2).sub.n OR.sup.3).sub.a-y

wherein M is Mg, Zn, and Al and mixtures thereof, R¹ and R³ are C₁ toC₁₈ hydrocarbyl, R² is hydrogen or methyl, n is a value from 1 to 20, yis a value between 0.01 and 1.0, and a is the valence of the metal.

Examples of these compounds are shown in Table III, below:

                  TABLE III                                                       ______________________________________                                        M.sup.a     R.sup.1     R.sup.2                                                                              R.sup.3                                                                             n    y                                   ______________________________________                                        Zn          C.sub.2 H.sub.5                                                                           H      CH.sub.3                                                                            6.4  1.0                                 Al          i-C.sub.4 H.sub.9                                                                         H      CH.sub.3                                                                            6.4  1.0                                 Mg           -n, .sub.- s-C.sub.4 H.sub.9                                                             H      CH.sub.3                                                                            6.4  1.0                                 Mg/Al = 2   C.sub.4 H.sub.9                                                                           H      CH.sub.3                                                                            6.4  1.0                                 Zn/Al = 1.5 C.sub.2 H.sub.5 /iC.sub.4 H.sub.9                                                         H      CH.sub.3                                                                            6.4  1.0                                 ______________________________________                                    

Thus, for example, a solution of ethylzinc-ω-methoxypolyethoxide in ahalocarbon solution was used to treat books and found to give a uniformdistribution of zinc in a page taken from the center of a book at alevel of 1.5-1.7% zinc oxide.

Other such typical alkylmetal alkoxides which may be used alone or incombination with each other in solution form to deacidify and strengthencellulosic materials are butylmagnesium ω-methoxypolyethoxide,isobutylaluminum bis-ω-methoxypolyethoxide and ethylzincbutoxytriglycolate.

It should be noted that the aluminum compounds, generally should not beused alone since they have a strong propensity toward hydrolysis.

In some cases it has been found that combinations of two or more of suchalkylmetal alkoxides possess improved properties. Thus, for example,addition of an equivalent amount ofisobutylaluminum-bis-ω-methoxypolyethoxide tobutylmagnesium-ω-methoxypolyethoxide pacifies the latter's normalreactivity with halocarbon compounds to such an extent that a solutionof these two metal alkoxides can be prepared containing a highconcentration of Freon TF.

In some cases, these alkylmetal alkoxides may act to improve thesolubility of the carbonated magnesium and zinc alkoxides in certainsolvents such as Freon TF. Thus, for example, addition of an equalamount of isobutylaluminum bis-ω-methoxypolyethoxide to zincbismethoxypolyethoxide solubility in Freon TF. By contrast, a Freon TFsolution of aluminum isopropoxide did not promote the solubility ofmagnesium ethoxide in the same solvent. Such blends of metal alkoxidesgive deacidifying media which are milder buffers than magnesiumalkoxides alone.

Also contemplated are the halometalalkoxides, X_(y) M^(a) OR_(a-y).(R'OH), wherein X is a halogen, preferably chlorine or bromine, M is ametal of Periodic Groups IIA, IIB, or IIIA, OR is an alkoxy groupwherein R is an alkyl, cycloalkyl, aryl, arylalkxl or alkylaryl, or analkoxyalkoxy group, particularly an 2-alkoxyalkoxy- orω-alkoxypoly(alkoxy) group, a is the valence of the metal, y is a valuefrom 0.01 to about 1 and X is 0 to 2.

Examples of such halometalalkoxides are chloromagnesium butoxyethoxide,chloromagnesium ω-methoxypolyethoxide, chlorozinc ω-methoxypolyethoxid,chloroaluminum bis-ω-butoxytriglycolate, and mixtures thereof.

A novel procedure for preparing such halometal alkoxides has beendeveloped which involves reaction of the desired alcohol and metal inthe presence of a minor quantity of methanol, and an equivalent quantityof fluorochlorocarbon such as 1,1,2-trifluorotrichloroethane (Freon TF)in a hydrocarbon solvent. The halocarbon functions as a halogenatingagent in the process:

    M.sup.a +ROH+0.5F.sub.2 ClC--CFCl.sub.2 →ClM.sup.a (OR).sub.a-1 +0.5F.sub.2 C═CFCl

The hydrocarbon solution is filtered and stripped, if desired, to giveresidual liquid products, which can be redissolved in various solvents,described above.

Also contemplated are acyloxymetal alkoxyalkoxides, (R⁴ C(O)O)_(y)M(--OCH(R²)CH₂ --OCH(R²)CH₂ --_(n) OR³)_(2-y).(R'OH)_(x) andalkoxypolyalkoxides in which R⁴ is a C₁ to C₁₈ alkyl, aryl, cycloalkyl,arylalkyl, or alkylaryl group, M is a divalent metal from Groups IIA andIIB of the Periodic Table, R' is a C₁ to ₁₈ alkyl, aryl, cycloalkyl,arylalkyl, or alkylaryl group, or is alkoxyalkoxy or alkoxypolyalkoxyderived from the alkoxide, where R² is methyl group or hydrogen and R'and R" are the same or different alkyl, aryl, cycloalkyl, aryalkyl andalkylaryl, y is a value from 0 to about 1 and x is a value from 0 to 2.

Also contemplated are magnesium and zinc mono- and dialkylaminoethoxidesand dialkylaminopoly alkoxides such as, e.g., magnesium or zincbis-N-methylaminoethoxide and magnesium or zincbis-N,N-dimethylaminoethoxide, and their higher homologs

    R.sup.3.sub.2 N(CH.sub.2 CH(R.sup.2)O--.sub.n CH.sub.2 CH(R.sup.2)OMOCH(R.sup.2)CH.sub.2 --OCH(R.sup.2)CH.sub.2--m NR.sup.3.sub.2. (R.sub.2 NH).sub.x

where n and m are greater than 1 and R² may be H or CH₃ and R¹, and R³may be the same or different C₁ -C₁₈ hydrocarbyl groups.

The following examples further illustrate the invention.

EXAMPLES Example I Preparation of Carbonated Magnesiumn-Hexyloxyethoxide

    C.sub.6 H.sub.13 OCH.sub.2 CH.sub.2 CH.sub.2 O--Mg--OC(O)OCH.sub.2 CH.sub.2 O--C.sub.6 H.sub.13                                       ("A")

To a solution of 292.5 g (2.0 mole) of ethyleneglycol, monohexyl ether(n-hexylcellosolve) dissolved in 850 ml heptane was slowly added 1.02liters of a solution of dibutylmagnesium in heptane (19.2 weightpercent). After reaction was complete, the solution was filtered andcarbon dioxide passed into it through a gas inlet tube from a one literflask containing pieces of dry ice. The gas was passed through twodrying columns containing calcium chloride before entering the gas inlettube. The temperature of the solution in the flask rose from 31° to 42°C. during the carbonation. After reaction was complete, as noted by asignificant drop in the reaction temperature, the solution was strippedof solvent on a ROTO-VAC apparatus and the residual fluid, somewhatviscous mass, transferred to a pint bottle under inert gas (argon). Theweight of recovered product was 307 g (87% recovery).

Another 0.11 mole preparation of magnesium n-hexyloxyethoxide usingmagnesium ethoxide in place of dibutylmagnesium was carried out and thesolvents (ethanol and heptane) removed by vacuum stripping. The viscousresidue was redissolved in hexane (to about 0.9M) and carbonated asdescribed above. The temperature during carbonation rose from 24.3° to39.8° C. After 1.25 hours of slow CO₂ feed, the temperature had returnedto 23° C. The solution was vacuum stripped to give a viscous mobileliquid that readily dissolved in hexane. Only a trace (<0.01%) ofethanol remained. An infrared scan of the residue dissolved in hexaneshowed a strong absorbence at 6 microns indicative of a carbonyl group.Analysis of the solvent-stripped residue for contained CO₃ gave a valueof 16.5%, corresponding to a CO_(3/) Mg ratio of 1.01.

Example II Preparation of Carbonated Maonesium Hexyloxyethoxyethoxide

    C.sub.6 H.sub.13 (OCH.sub.2 CH.sub.2).sub.2 --OMg--OC(O)O(CH.sub.2 CH.sub.2 O).sub.2 --C.sub.6 H.sub.13                               ("C")

To 71.5 ml of a 27.4 weight percent solution of dibutylmagnesium inheptane (0.1 mole) in 100 ml of hexane was slowly added 41 ml (0.2 mole)of hexylcarbitol (neat). A clear, viscous solution was obtained uponcooling to room temperature. Carbonation of the solution with carbondioxide gas thinned out the solution considerably. The resulting productwas stripped of solvent to give 35 grams of a fairly fluid, somewhatviscous clear yellow mobile (pourable) liquid (87% recovery).

Example III Preparation of Carbonated Ethoxymagnesiumω-Methoxypolyethoxide

    C.sub.2 H.sub.5 OC(O)Og--OCH.sub.2 CH.sub.2 --OCH.sub.2 CH.sub.2--6.4 OCH.sub.3                                                 ("D")

To 71.5 ml of a 27.4 weight percent solution of dibutylmagnesium inheptane (0.1 mole) contained in 100 ml of toluene was slowly added 30 ml(0.093 mole) of methoxypolyethyleneglycol (CH₃ O--CH₂ CH₂ O--₇.4 H,Union Carbide Corp. MPEG 350). A clear, slightly hazy solution of thealkyl magnesium alkoxide resulted.

Two 10 ml aliquots of the solution (approx. 0.004 mole each) were takenand treated as follows:

(a) Carbonated with CO₂ --a clear very fluid solution was obtained oncarbonation.

(b) Alkoxylated with ethanol. Sufficient ethanol

0.2 ml) was added to the aliquot to dissipate the red color generated bya small amount of 2,2-biquinoline indicator. A thick, extremely viscousclear solution resulted, which on subsequent carbonation thinned outalmost immediately to give a pale yellow clear, non-viscous solution.

Treatment of the remainder of the main alkylmagnesium alkoxide solutionas in (b) above, followed by solvent stripping of the carbonatedmagnesium alkoxide solution yielded 34 grams of a pale yellow, slightlyhazy, mobile, somewhat viscous but pourable, liquid residue, whichdissolved readily in toluene, but not in hexane. To 8.3 grams ofcarbonated ethoxy magnesium-ω-methoxypolyethoxide was added 45 ml ofFreon TF to give a 2 phase mixture. Addition of 0.8 grams ofbutoxytriglycol gave an almost clear solution, while a further additionof 0.8 g of butoxytriglycol gave a clear solution. Thus, as little as20-50 mole % (10-25 wt %) of butoxytriglycol will promore solubility ofethoxy magnesium-ω-methoxypolyethoxide in Freon TF.

In the "D" above, carbonation could as well have been shown to takeplace on the methoxy-ω-polyethoxide side of the molecule.

Example IV Preparation of Carbonated Magnesium Butoxytriglycolate

    C.sub.4 H.sub.9 O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.2 CH.sub.2 OMgOC(O)OCH.sub.2 CH.sub.2 O--CH.sub.2 CH.sub.2).sub.2 OC.sub.4 H.sub.9("B")

(a) 25 mls (0.031 mole) of 1M dibutylmagnesium in hexane solution plusan additional 50 ml of hexane was slowly added 12.8 g purebutoxytriglycol (Union Carbide Corp.). The solution remained clear andfluid throughout. After approximately 0.5 hours, carbon dioxide waspassed through the solution to form the alkoxide carbonate. The finalsolution was clear and fluid at about 0.35M Mg and was solvent strippedon the ROTO-VAC apparatus for 1 hour at 70° C. The concentrated solutionwas viscous, but fluid (mobile). An infrared scan of a hexane solutionof the product showed a new band at 6.0 microns.

(b) To 27.7 grams (1.14 g.at.) of magnesium powder in 850 ml ofD-heptane activated with 0.2 g of iodine and heated to 90° was added 10ml of a mixture of 362 g (1.75 moles) of butoxytriglycol and 24 g (0.52mole) of ethanol. Reaction was slow, so an additional 15 g of magnesiummetal in the form of chips was added and heating resumed. After a time,reaction began slowly and mixed alcohol feed was continued. After thereaction was completed, about half the mixture was filtered (slowfiltration) to give a rather viscous, clear, yellow solution. Theremainder of the unfiltered mixture was carbonated and the resulting mixbecame quite fluid and was easily filtered. After carbonation of thefirst half of the solution (thinning of solution), the solutions werecombined and solvent-stripped to yield 368 grams of a viscous, butmobile, pourable product.

The carbonated solution of magnesium butoxytriglycolate in heptane priorto stripping was approximately 0.9 molar in magnesium concentration, butabout 50 weight percent in carbonated product, showing the highconcentrations of these magnesium compounds attainable. Some of themagnesium butoxytriglycolate from a previous run, which had not beencarbonated, was also solvent stripped. The resulting product wasextremely viscous (not mobile) even with the addition of 20% by weightof hexane, thus demonstrating the unexpected decrease in viscosity ofthese magnesium alkoxide solutions on carbonation.

The carbonated product was analyzed for carbonate (CO₃) content andfound to contain 16.21 weight percent which corresponded to a CO₃ /Mgratio of 1.02. Infrared analysis showed a strong absorption in the6.0-6.1 micron frequency region.

Example V Preparation of Carbonated Magnesium Butoxy 2-Propoxide

    C.sub.4 H.sub.9 OCH.sub.2 CH.sub.3)OMgOC(O)OCH.sub.3)CH.sub.2 OC.sub.4 H.sub.9

0.025 Mole (18 ml) of 27.4 weight percent DBM in heptane and 25 ml ofhexane were placed in a flask and 7.5 ml (0.05 moles) ofbutoxy-2-propanol Propasol B (Union Carbide Propasol B,MW=132.2,d=0.8843) added dropwise with stirring. The solution remainedhazy almost throughout the addition, then cleared up near the end of theaddition to give a clear colorless, somewhat viscous solution. Theproduct was carbonated and the viscosity of the solution appeared todecrease as evidenced by the greater stirring speed of the magneticstirring bar.

Example Vi Preparation of Carbonated Hexyloxyethoxymagnesium ω-Methoxypolyethoxide (MPEG 350)

    C.sub.6 H.sub.13 OCH.sub.2 CH.sub.2 OC(O)OMgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2--6.4 OCH.sub.3

To 0.25 mole (18 ml) of 27.4 weight percent dibutylmagnesium solution inheptane (DBM) and 25 ml of hexane, was slowly added 8 ml (0.025 mole) ofMPEG 350 (Union Carbide Methoxypolyethylene glycol, MW=335-365). Next4.1 ml (0.025 mole) of hexylcellosolve was aoded to yield a milkysolution which slowly separated into two clear, colorless, mobile liquidlayers. Next, the following amounts of DBM and hexylcellosolve (HC) wereadded in consecutive fashion: 9 ml (0.0125 mole) DBM, 4.1 ml (0.025mole) HC, 9 ml DBM, 4.1 ml HC, 4.5 ml DBM, 2.05 ml HC, 4.5 ml DBM, 2.05ml HC. The total DBM added to this point was 0.0625 mole, totalhexylcellosolve was 0.100 mole and MPEG 350, 0.025 mole (ratioHC/MPEG=4.0). A clear, colorless solution was obtained at warmer thanroom temperatures, but a small amount of a second phase separated oncooling to room temperature. On carbonation, some decrease in viscositywas noted, but solvent evaporation occurred during carbonation to give aslightly viscous, approximately 1 molar solution which was crystal clearand colorless even at room temperature. In the formula above,carbonation could as well have been shown to take place on the methoxyω-polyethoxide side of the molecule.

Example VII Preparation of Carbonated HexyloxyethoxyethoxymagnesiumωMethoxypolyethoxide

    C.sub.6 H.sub.13 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC(O)OMgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2--6.4 OCH.sub.3

To 0.025 mole (18 ml) of DBM (27.4 weight percent in heptane) and 25 mlhexane was slowly added 8.1 ml (0.040 mole) of diethylene gylcolmonohexyl ether (Hexyl Carbitol™ UCC) followed by 3.2 ml (0.01 mole) ofMPEG 350. A clear, pale yellow fluid solution was obtained which, oncarbonation, became even more fluid (less viscous). In the formulaabove, carbonation could as well have been shown to take place on themethoxy ω-polyethoxide side of the molecule.

Example VIII Preparation of Carbonated Magnesium Propoxy 2-Propoxide

    C.sub.3 H.sub.7 OCH.sub.2 CH(CH.sub.3)OMgOC(O)OCh(CH.sub.3)CH.sub.2 OC.sub.3 H.sub.7

To 0.025 mole (18 ml) of DBM (27.4 weight percent) and 25 ml hexane wasslowly added 6.6 ml (0.05 mole) of propoxy 2-propanol (UCC Propasol P).The solution remained hazy almost throughout the addition, then clearedup to give a colorless, slightly viscous, mobile solution. Carbonationdecreased the viscosity of the solution.

Example IX Preparation of Zinc Hexyloxyethoxyethoxide

    C.sub.6 H.sub.13 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OZnOCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.13

To 50 ml of a 14.4 weight per cent solution of deethylzinc in hexane(density =0.708) was added 16.8 ml (15.7 g, 0.082 m) hexyl carbitol(Union Carbide). Ethane was evolved during the addition and thetemperature of the reaction mixture reached 55°-60° C. After additionwas complete, the mixture was heated to reflux for 30 minutes and thensolvent was stripped on a ROTO-VAC unit to 80° C. under full vacuum (<1min.). A deep amber, clear, viscous, but quite mobile liquid wasobtained. Carbonation of a solution of this product in hexane at roomtemperature did not form a carbonate as evidenced by CO₂ evolution ontreatment with aqueous HCl.

A repeat of the above preparation using milder temperatures (<30° C.)yielded a light yellow colored, less viscous product.

Exampel X Preparation of Aluminum Hexyloxyethoxyethoxide

    Al(OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.6 H.sub.13).sub.3

A volume of 27 ml (25 g, 0.1325 m) of hexyl carbitol (Union Carbide) wasadded slowly to a solution of 50 ml of 25 weight per centtriisobutylaluminum in hexane (density 0.70). Isobutane was evolved andthe solution heated to 55-60° C. The reaction mixture was then refluxedfor 30 minutes and stripped of solvent under vacuum in a ROTO-VAC unit.The residual product was a fluid, slightly viscous, light yellow coloredoil (24.5 grams).

Example XI Preparation of Carbonated Magnesium-bis-ω-methoxypolyethoxide

    CH.sub.3 O(CH.sub.2 CH.sub.2 O).sub.6.4 CH.sub.2 CH.sub.2 OMgOC(O)OCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.6.4 OCH.sub.3

To 50 ml of a 1.3 molar solution of dibutylmagnesium in heptane (0.065m) and 70 ml of toluene containing a small amount of 2,2'-biquinolineindicator, was added, slowly, 42 ml (46 g) of methoxypolyethylene glycol(Union Carbide MPEG 350) with stirring and cooling to a somewhat hazy,light yellow solution. The product was then treated with dry carbondioxide gas for approximately one hour to give a clear solution. Thesolution was stripped under vacuum to a yellow-green, somewhat hazymobile, viscous liquid (41.5 g).

A solution of this product in Freon TF could be prepared by admixture ofas little as 14 wt % (50 mole %) of butoxytriglycol.

Example XII Preparation of CarbonatedButoxytriglycoxymagnesium-ω-methoxypolyethodie

    C.sub.4 H.sub.9 O(CH.sub.2 CH.sub.2 O).sub.2 CH.sub.2 CH.sub.2 OC(O)OMgOCH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2--6.4 OCH.sub.3

(a) To 54 ml of a 1.3 molar solution of dibutylmagnesium in heptane and50 ml of toluene was added 22.4 ml (24.5 g, 0.07 m) ofmethoxypolyethylene glycol (MPEG 350, Union Carbide) and 14.4 ml (14.4g, 0.07 m) of butoxytriglycol (Union Carbide). The solution stayed clearand fluid throughout the addition. The solution was carbonated to give aclear, fluid light colored solution. After stripping under vacuum toremove solvent, a weight of 43.7 g was obtained, which readily dissolvedin Freon TF.

In the above formula, carbonation could have been shown to take place onthe ω-methoxypolyethoxide group.

Example XIII Preparation of Ethyl Zinc ω-methoxypolyethoxide (EZMPG)

    C.sub.2 H.sub.5 ZnOCH.sub.2 CH.sub.2 --OCH.sub.2 --CH.sub.2 O).sub.6.4 OCH.sub.3

To 121 ml of a 14.4 weight percent solution of diethylzinc in hexane(0.10 mole) was added slowly, 31.9 ml (35 g, 0.10 mole) ofmethoxypolyethylene glycol (MPEG 350, Union Carbide), keeping thetemperature below 30° C. with cooling. After stirring for an additional45 minutes, the milky solution (2 layers) was vacuum stripped to removehexane (only one liquid layer after strip). A grayish hazy liquid (39 g)was obtained which was dissolved in toluene, the solution was allowed tosettle, and the clear supernatant decanted and again stripped to removetoluene. 35 g of an almost clear, water white fluid product wasobtained, which slowly gave off a gas (bubbled) on hydrolysis orexposure to air, but did not spontaneously ignite. To 33 grams of EZnMPGwas added 100 ml of Freon TF to give a slightly hazy solution.

Example XIV Prepara5tion of Isobutylaluminum-ω-methoxypolyethoxide

    C.sub.4 H.sub.9 Al(OCH.sub.2 CH.sub.2 --OCH.sub.2 CH.sub.2 --.sub.6.4 OCH.sub.3).sub. 2

To 113 ml of a 25 weight per cent solution of triisobutylaluminum inhexane (0.10 mole) was slowly added 69.4 ml of methoxypolyethyleneglycol (MPEG 350, Union Carbide). The solution became milky andeventually formed two layers. Addition of 75 ml of toluene gave a clearsolution. The solution was then vacuum stripped to remove solvents. Afluid, colorless, slightly hazy liquid (68 g) was recovered, whichreadily dissolved in Freon TF to give a clear solution.

Example XV Preparation of Butylmagnesium ω-methoxypolyethoxide

    C.sub.4 H.sub.9 MgOCh.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2 --.sub.6.4 OCH.sub.3

To 113 ml of a 0.97 m solution of dibutylmagnesium in heptane and 50 mlof toluene was added, with cooling, 35 ml (0.11 m) of MPEG 350 (UnionCarbide). The mixture was then stirred for 2 hours and allowed to settleovernight. Two liquid layers were obtained, the lower layer containing92% of the magnesium content. The upper layer was separated anddiscarded. 20 ml of toluene was added and the lower layer was vacuumstripped to give a clear orange-colored viscous liquid (42.3 g), whichwas very reactive to air and moisture, but not pyroforic. It reactedvigorously with Freon TF. However, when mixed with an equivalent amountof Isobutylaluminum ω-methoxypolyethoxide, only a very slight, if any,reaction with Freon TF was noted, indicating passivation of thecarbon-magnesium bond and good solubility in Freon TF with potential forbook deacidification.

Example XVI Preparation of Carbonated Zinc bis-ω-methoxypolyethoxide

    CH.sub.3 O--CH.sub.2 --CH.sub.2 O--.sub.6.4 CH.sub.2 CH.sub.2 OZnOC(O)OCh.sub.2 --OCH.sub.2 CH.sub.2 --.sub. 6.4 OCH.sub.3

To a volume of 139 ml (0.115 mole of a 14.4 weight percent solution ofdiethylzinc (DEZ) in hexane and 75 ml toluene was slowly added 80.5 g(0.23 mol) of methoxypolyethylene glycol (Average Mol. Wt=350) at25°-30° C. The mixture (2 layers) was stirred 45 minutes after the DEZaddition was complete. The product mixture was vacuum stripped to removesolvent, but became extremely viscous and would not flow. The productmass was redissolved in hot toluene (40°-50° C.) and carbonated. Heatwas generated as carbonation proceeded. The product solution was againvacuum-stripped to give a much less viscous, pourable product.

An infrared spectrum of the neat product showed bands at 5.15 (ms), 5.40(ms), 5.55 (ms), 5.75(w), and 6.25 (s) microns, all indicative ofcarbonyl groupings. There were no absoprtions in the 2.7-3.25 micronsregion indicative of hydroxyl groups. The product was not soluble inFreon TF; however, addition of 5 volume per cent chloroform gave a clearsolution containing 5 with an equal volume of isobutylaluminumbis-ω-methoxypolyethoxide followed by Freon TF addition gave a fluidupper layer containing 67 vol % of metal MPEG compounds in Freon TF,indicating a solubilizing assistance of the aluminum compound.

Example XVII Preparation of Carbonated Methoxymagnesiumω-ethoxytriglycolate in Freon TF

0.131 moles (11.30 g) of Mg(OCH₃)₂, 85 ml of Freon TF and 0.131 moles(23.2 g, 23 ml) of of ethoxytriglycol (Union Carbide Corp.) were mixedtogether and stirred for 30 minutes. Carbon dioxide was sprayed into thethick mass, causing the mix to thin and to become almost clear. Anadditional 40 ml of Freon TF was added along with 13.5 ml (0.066 moles)of butoxytriglycol and the solution diluted to 650 ml with Freon TF togive a 0.2 molar solution of the title compound.

Comparison Freon TF Solubiilty Test Magnesium Ethoxide/AluminumIsopropoxide

One gram (5 mmoles) of aluminum ispropoxide was dissolved in 10 ml ofFreon TF solvent and 0.7 grams (6 mmoles) of magnesium ethoxide added.After mixing in an ultra-sonic bath, followed by settling of suspendedmatter, 3 ml of the clear solution was analyzed for Mg and Al. TheoryAl: 1.5 mmole, Found Al: 1.5 mmole. Theory Mg: 1.8 mmoles, Found Mg:0.08 mmoles. Conclusion: Little effect of Aluminum alkoxide onsolubility of Magnesium alkoxide in Freon TF, and therefore not a usefulsystem for deacidification of books.

General Description of the Gas Expansion and Deacidification Experiments

Basically, the gas expansion experiments were carried out in two typesof apparatus. First, a small amount of the metal compound to be testedwas dissolved in the desired solvent to an approximately 10% (by volume)level, and solubility tests run in a Jurgeson Gauge with the desiredexpander gas (see description below). If a reasonable expansion wasevidenced on pressurization with the gas without precipitation of thecompound, further testing was carried out on 3 inch by 3 inch sectionsof books (generally pre-dried before treatment) in a 3 liter steelpressure vessel.

The first type of test apparatus was a Jurgeson Gauge connected to asource of pressurized gas. The Jurgeson Gauge is essentially a steamboiler sight glass in which volume expansions of samples by test gascould be readily observed and measured. The sample, usually dissolved ina compatible solvent, is transferred under inert gas into the bottom ofthe gauge, its liquid level height measured (1,2,3 "bolts" on the frontof the gauge) and the desired test gas pressured in slowly, measuringthe volume expansion of the liquid samples as the pressure is increasedincrementally. Generally, at some specific pressure and volume, thesample product becomes insoluble in the expanded solvent medium andprecipitates. Then, as the pressure is slowly released from the system,the product redissolves. In this way, the solubility parameters for eachtest gas and sample solution combination can be measured and optimumbook treatment conditions determined.

The three samples tested were given letter designations A, B, and C andwere essentially free of solvent. Sample A was product from EXAMPLE I,Sample B was product from EXAMPLE IV (b), Sample C was product fromEXAMPLE II, and Sample D was product from EXAMPLE III.

Experiments with Carbon Dioxide as "Expander" Gas

A test was run in the Jurgeson Gauge with a solution of Sample C inhexane (approximately 33 weight percent), pressurizing with CO₂ to about900-1000 psi, less than a doubling of volume resulted before theinception of precipitation of product from solution. Exhaustion of gaswith pressure reduction caused dissolution of the precipitated product.A 10 volume percent solution of Sample C in perchlorethylene,pressurized to 870 psi with CO₂, doubled in volume. The equivalent zincand aluminum salts in perchlorethylene also showed this doubling effect.

Sample A solubilized well in Freon TF (20 weight percent) and a test wasrun with it and CO₂ in the Jurgeson Gauge. As the pressure was increasedto Ca 500 psi, a thick viscous mass was formed in the gauge, whichreverted back to a fluid solution on release of pressure. On running thesame test with hexane in place of Freon TF, reversible precipitationoccurred, but no thickening.

Sample B solubilized well in perchlorethylene, and a 10 volume percentsolution was expanded with CO₂ to about 700 psi in the Jurgeson Gaugewith an apparent doubling of the original solution volume before therewas any indication of precipitation. In hexane, only about a 30% volumeexpansion occurred at about 600 psi before precipitation was noted.

Both pre-dried and undried 3 inch by 3 inch by 1 inch sections of an oldbook were treated with a CO₂ expanded (650 psi) 10 vol percent solutionof Sample B in perchlorethylene (400 ml) in a 3 liter tubular pressurevessel for 10 minutes at room temperature. The books were positionedjust above (1/4 to 1/2 in.) the level of the liquid prior topressurization with CO₂. The pressure was first increased to 500 psi andthe liquid drained off, then the pressure bled off to zero. The vesselwas once again pressured (to 1000 psi) with CO₂ for a few minutes andthen the pressure released (CO₂ "rinse"). The undried book exhibited awhite residue on the inside and outside of the covers and the pagesclose to the covers, with a "dusting" effect throughout. The pre-driedbook showed no evidence of a white residue or any dusting. A page takenfrom the center of the pre-dried treated book was sprayed with a pHindicator solution and showed that an even distribution of deacidifyingagent had been deposited thereon. ICP analysis for % Mg (as MgCO₃) of apage taken from the center of the book and cut into quarters gave thefollowing results: Upper left quarter: 1.05; upper right quarter: 1.40;lower left quarter: 0.91; lower right quarter: 1.12. These results alsoindicated a fairly even deposition of deacidifying compound into thebooks. Cold water extraction (70 ml) of 1 gram of the pages taken fromthe center of the book (TAPPI T-509) gave a pH value of 8.3.

A rough comparison of the strength of the treated vs. untreated pagestaken from the center of the book was made by determining the number oftimes the pages could be folded back and forth (fold axis parallel toiinding) before breakage and separation. The untreated page showed only3 folds to break, the treated, 21.

Experiments with Ethane as "Expander" Gas

Tests were run in the Jurgeson Gauge using Compound A solubilized inhexane, but with ethane as the expanding gas.

With an 8.6% solution of A in hexane, a precipitate was noted at Ca 600psi. This test was repeated enclosing a sheet of rolled up paper in thegauge, set above the initial liquid level in the gauge (beforepressuring with ethane). After expansion of the liquid level onto thepaper surface and precipitation of product, the paper strip showedstriations on testing with pH paper indicating coalescence of thedroplets of viscous product and uneven deposition onto the paper. Thetest was repeated at an ethane pressure below 500 psi which did notcause precipitation of the product, but which was sufficient to expandthe solution volume to cover part of the test paper strip. After releaseof pressure, a dry paper was obtained. The immersed section of papershowed an even distribution of product onto the strip (pH indicator)giving the paper a satiny, smooth feel.

Another sample of A was dissolved in hexane (6 vol percent) and used totreat an old pre-dried book in the 3 liter pressure vessel using ethaneas the expander gas (500 psi). The book was positioned above the liquidlevel before pressurization. Treatment time was approximately oneminute. After drying, a treated page was cut into quarters and analyzedfor % Mg (as MgCO₃) in each quarter. Results were as follows: Upper leftquarter: 0.35; upper right quarter: 0.95; lower left quarter: 1.02;lower right quarter: 1.61. Even for only such a short treatment period,a significant deposition of magnesium had occurred in the book.Obviously, a longer treatment time is required for even depositionthroughout the book.

Paper/Book Treatment Experiments Immersion at Atmospheric Pressure

The solution (approximately 5 vol/vol %) of EZMPG in Freon TF/PERC inEXAMPLE XIII was used to treat predried 3 inch by 3 inch by 0.5 inchsection of paperback novel by immersion in the circulating solution fora period of 20 minutes. After removal of the solution and drainage ofany excess, the wet book was dried by stripping under vacuum (35°-40°C.) for a period of two hours. A pH indicator so was sprayed onto a pageof the book taken from the center and indicated an even distribution ofdeacidifying agent had been deposited. pH measurement by the TAPPI T-509Cold Water Extraction test showed a pH of 8.0 (vs. 6.3 in an untreatedbook). Determination of evenness of deposition of deacidifier by ICPmeasurement of zinc (expressed as % ZnO) in a center page of the bookcut into four equal squares gave the following results: Upper leftcorner: 1.43; upper right corner: 1.70; lower left corner: 1.48; lowerright corner: 1.70. The untreated book showed no more than 0.005% ZnO inany square.

An 8 vol % solution of Compound B (EXAMPLE IV (b)) in Freon TF wasprepared by adding 600 ml of solvent to 49.4 grams of B. The solutionwas used to treat books and pages from these books under a variety ofconditions:

(a) Single oaoe treatment: Triangular, free-standing forms were made upof three pages taken from a pre-dried book and stapled together. Thisoorm was placed in the treatment unit, treated for various times withthe above TF solution of B, then dried by vacuum stripping. The drypages were separated, and tested for (a) pH by Cold Water Extraction(TAPPI T-509), percent magnesium distribution in the quartered page byICP, and number of folds to break (strength). The following Table showsthe results obtained:

    ______________________________________                                                                   % Mg (ICP) in quartered                            Treatment Time   Folds to  page (as MgCO.sub.3)                               min.       pH    Break     UL   UR    LL   LR                                 ______________________________________                                        2          8.6    4        2.13 2.03  2.31 2.28                               5          8.7   16        2.31 2.35  2.52 2.59                               10         9.1   30        2.87 2.84  2.84 2.73                               ______________________________________                                         UL = upper left; UR = upper right; LL = lower left; LR = lower right     

The results indicated that longer treatment times improved the strengthof the page as well as the evenness of distribution and amount ofdeposited deacidifying agent in the page.

Further single page fold endurance tests were run comparing treatedsolution B in Freon TF with (a) CarbonatedButoxytriglycoxymagnesium-ω-methoxypolyethoxide (compound of EXAMPLEXII) in Freon TF (7.2 vol %), and (b) CarbonatedMagnesium-bis-ω=methoxypolyethoxide (compound of EXAMPLE XI) inperchlorethylene (8.3 vol %).

Single 3 inch by 3 inch pages from an old book were stapled together asbefore and treated with the above solutions.

Results of the tests are as follows:

    ______________________________________                                                          No. of folds to break                                       Solution          (Avg 3 tests)                                               ______________________________________                                        B in TF           29                                                          Comp'd of EX. XII in TF                                                                         35                                                          Comp'd of EX. XI in PERC                                                                        59                                                          Untreated          7                                                          ______________________________________                                    

These results indicate that longer poly(ethoxy) chains (7 ethoxy unitsin chain) impart greater strength to the pages than shorter chains (3ethoxy units in the chain).

(b) Book Treatment: 3 inch by 3 inch by approximately 1 inch sections ofan old book (both pre-dried and undried) were placed in the treatmentvessel under inert gas (argon) and covered with the Freon TF solution ofB used in (a) above. After 10 minutes, the treated solution waswithdrawn, the books allowed to drain (15 minutes), and a vacuum applied(<1 mm) with exernal heating to about 35-40° C. for 2 to dry the books.After returning the system to atmospheric pressure, the books wereexamined and tested as follows:

(i) Appearance: Undried book: white powdery patches on outside andinside of cover and throughout book. Pages have a powdery feel. Driedbook: no white patches or powdery feel. Book appears unchanged frominitial stte.

(ii) pH (center page): undried book--8.6; dried book --8.7.

(iii) % Mg distribution (center page) as MgCO₃ :

Undried book: UL-2.14; UR-1.79; LL-1.96; LR-1.75.

Dried book: UL-1.44; UR-1.44; LL-1.51; LR-1.54.

These results indicate that although deposition of idifier is greater inan undried book, as compared to a dried book, the deacidifier is not asevenly deposited, nor is it all deposited within the structure of thepages, i.e., some deacidifier is reacted with surface water and formsfree (dusty) magnesium hydroxide, which is unacceptable. Pre-dried bookswere deacidified more evenly and completely and showed no obvious changein appearance before and after treatment.

    __________________________________________________________________________    (R.sup.4 O(CH.sub.2 CH(R.sup.2)O).sub.n CH.sub.2 CH(R.sup.2)O).sub.y          M(OC(O)OCH(R.sup.2)CH.sub.2 (OCH(R.sup.3)CH.sub.2).sub.m OR.sup.3).sub.2-y    .(R.sup.1 OH).sub.x                                                           and                                                                           (R.sup.4 O(CH.sub.2 CH(R.sup.2)O).sub.n CH.sub.2 CH(R.sup.2)OC(O)O).sub.y     M(OCH(R.sup.2)CH.sub.2 (OCH(R.sup.2)CH.sub.2).sub.m OR.sup.3).sub.2-y.(R.s    up.1 OH).sub.x                                                                M  R.sup.4                                                                            R.sup.2                                                                           R.sup.3                                                                            R.sup.1         m  n  y  x                                   __________________________________________________________________________    Mg C.sub.6 H.sub.13                                                                   H   C.sub.6 H.sub.13                                                                   --              0  0  1.0                                                                              0                                   Mg C.sub.6 H.sub.13                                                                   H   C.sub.6 H.sub.13                                                                   --              1.0                                                                              1.0                                                                              1.0                                                                              0                                   Mg C.sub.4 H.sub.9                                                                    H   C.sub.4 H.sub.9                                                                    --              2.0                                                                              2.0                                                                              1.0                                                                              0                                   Mg C.sub.4 H.sub.9                                                                    CH.sub.3                                                                          C.sub.4 H.sub.9                                                                    --              0  0  1.0                                                                              0                                   Mg C.sub.6 H.sub.13                                                                   H   CH.sub.3                                                                           --              6.4                                                                              0  1.6                                                                              0                                   Mg C.sub.6 H.sub.13                                                                   H   CH.sub.3                                                                           --              6.4                                                                              1.0                                                                              1.6                                                                              0                                   Mg C.sub.3 H.sub.7                                                                    CH.sub. 3                                                                         C.sub.3 H.sub.7                                                                    --              0  0  1.0                                                                              0                                   Zn C.sub.6 H.sub.13                                                                   H   C.sub.6 H.sub.13                                                                   --              1.0                                                                              1.0                                                                              1.0                                                                              0                                   Mg CH.sub.3                                                                           H   CH.sub.3                                                                           --              6.4                                                                              6.4                                                                              1.0                                                                              0                                   Mg C.sub.4 H.sub.9                                                                    H   CH.sub.3                                                                           --              2.0                                                                              6.4                                                                              1.0                                                                              0                                   Zn CH.sub.3                                                                           H   CH.sub.3                                                                           --              6.4                                                                              6.4                                                                              1.0                                                                              0                                   Mg CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2)--CH.sub.2 CH.sub.2                       --              6.4                                                                              6.4                                                                              1.0                                                                              0.5                                 __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________    (R.sup.4 O).sub.y M(OC(O)OCH(R.sup.2)CH.sub.2 (OCH(R.sup.2)CH.sub.2).sub.n     OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                                         and                                                                           (R.sup.4 O(O)CO).sub.y M(OCH(R.sup.2)CH.sub.2 (OCH(R.sup.2)CH.sub.2).sub.n     OR.sup.3).sub.2-y.(R.sup.1 OH).sub.x                                         M  R.sup.4                                                                          R.sup.2                                                                          R.sup.3                                                                          R.sup.1        n   y  x                                           __________________________________________________________________________    Mg C.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                         --             6.4 1.0                                                                              --                                          Mg CH.sub.3                                                                         H  C.sub.2 H.sub.5                                                                  CH.sub.3.sup.(1)                                                                             2.0 1.0                                                                              1.0                                                     C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2 --) .sub.2CH.sub.2                        CH.sub.2 --           0.5                                         Mg CH.sub.3                                                                         H  C.sub.4 H.sub.9                                                                  CH.sub.3       2.0 1.0                                                                              1.0                                         Mg CH.sub.3                                                                         H  CH.sub.3                                                                         CH.sub.3.sup.(1)                                                                             2.0 1.0                                                                              1.0                                                     C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2 --) .sub.2CH.sub.2                        CH.sub.2 --           1.0                                         Mg C.sub.2 H.sub.5                                                                  H  C.sub.4 H.sub.9                                                                  C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2 --) .sub.2CH.sub.2                        CH.sub.2 --    2.0 1.0                                                                              0.5                                         Mg C.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                         C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2 --) .sub.2CH.sub.2                        CH.sub.2 --    6.4 1.0                                                                              0.5                                         Mg C.sub.2 H.sub.5                                                                  H  CH.sub.3                                                                         C.sub.4 H.sub.9 (OCH.sub.2 CH.sub.2 --) .sub.2CH.sub.2                        CH.sub.2 --    6.4 2.0                                                                               0.27                                       __________________________________________________________________________     .sup.(1) R.sup.1 is mixture of the two groups, CH.sub.3 and C.sub.4           H.sub.9 (OCH.sub.2 CH.sub.2).sub.2 CH.sub.2 CH.sub.2 ---                 

We claim:
 1. A process for preparing fluid, low viscosity carbonatedmetal 2-alkoxy alkoxides and ω-alkoxypolyalkoxides comprising reactingin a solvent selected from liquid hydrocarbon solvents and liquidhalocarbon solvents a reactant selected from substituted metal 2-alkoxyand metal ω-alkoxypolyalkoxides of the formula

    (R.sup.4 O).sub.y M.sup.a (OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2 (CH.sub.2--n OR.sup.3).sub.a-y.(R.sup.1 OH).sub.x

    (R.sup.4 O(CH.sub.2 CH(R.sup.2)O)--.sub.n CH.sub.2 CH(R.sup.2)O--.sub.y M.sup.a (OCH(R.sup.2 CH(OCH(R.sup.2 (CH.sub.2 --.sub.m OR.sup.3).sub.a-y.(R.sup.1 OH).sub.x

wherein M is a metal selected from magnesium, zinc and mixtures of Mgand Zn, R² is selected from hydrogen and a methyl radical, R', R³ and R⁴are independently selected from alkyl groups containing 1 to 12 carbonatoms, y has a value from 0.01 to 1, x is a value from 0.001 to 2 and nand m have a value from zero to 100, with gaseous carbon dioxide.
 2. Theprocess of claim 1 wherein the alkoxide is selected from magnesiumbis-butoxytriglycolate, magnesium bis-ω-methoxypolyethoxide, zincbis-butoxytriglycolate, zinc bis-ω-methoxypolyethoxide, magnesiumbis-hexylcarbitolate, zinc bis-hexylcarbitolate, ethoxymagnesiumω-methoxypolyethoxide, methoxymagnesiumethoxytriglycolate,ethoxymagnesiumethoxytriglycolate, methoxymagnesiumbutoxytriglycolateand ethoxyzinc ω-methoxypolyethoxide.
 3. A composition comprising amixture of compounds selected from compounds of the formula

    (R.sup.4 O.sub.y M(OC(O)OOCH(R.sup.2 CH.sub.2 (OCH(R.sup.2)CH.sub.2 --.sub.n OR3).sub.2-y.(R.sup.1 OH).sub.x

    (R.sup.4 O(O)CO).sub.y M(OCH(R.sup.2 CH.sub.2 (OCH(R.sup.2)CH.sub.2 --.sub.n OR.sup.3.sub.2-y.(R.sup.1 OH).sub.x

wherein M is selected from Mg, Zn, mixtures of Mg and Zn, n is a valuefrom 1 to 20, R³ and R⁴ are C₁ -C₁₈ hydrocarbyl groups, R² is hydrogenor methyl and R¹ is the same or different R⁴ and/or R³ O(CH₂CH(R²)O--_(n) CH₂ CH(R² --, y is a value from 0 01 to one and x is avalue from zero to two.
 4. The composition of claim 9 wherein M ismagnesium, n is 6.4, R² is hydrogen, R³ is methyl, R⁴ is ethyl, R¹ is C₄H₉ O (CH₂ CH₂ O)₂ CH₂ CH₂ --, y is one and x is 0.2 to 0.5.
 5. Thecomposition of claim 9 wherein M is magnesium, R³ and R⁴ are selectedfrom methyl, ethyl and butyl, R² is hydrogen and R¹ is selected frommethyl, ethyl, butyl and a R³ O(CH₂ CH₂ O--CH₂ CH₂ - group in which R³is selected from methyl, ethyl and butyl groups, n is two, y is one andx is zero to two.
 6. The composition of claim 4 in which R³ is ethyl, R⁴is selected from methyl and C₄ H₉ O(CH₂ CH₂ O)₂ CH₂ CH₂ -- and x is 1.5.7. A composition comprising a mixture of compounds selected fromcompounds of the formula

    (R.sup.4 O(CH.sub.2 CH(R.sup.2)O).sub.n CH.sub.2 CH(R.sup.2)O).sub.y --M(OC(O)OCH(R.sup.2)Ch.sub.2 (OCH(R.sup.2)CH.sub.2).sub.m OR.sup.3).sub.2--y.(R'OH).sub.x

    (R.sup.4 O(CH.sub.2 CH(Rhu 2)O).sub.n CH.sub.2 CH(R.sup.2)OC(O)O).sub.y M(OCH(R.sup.2)CH.sub.2 OCH(R.sup.2)CH.sub.2).sub.m OR.sup.3).sub.2-y.(R'OH).sub.x

wherein M is selected from Mg, Zn, and mixtures thereof, n and m arevalues from 1 to 20, R² is hydrogen or methyl, R⁴ and R³ are C₁ -C₁₈alkyl groups, R' is the same or different or R³ O(CH₂ CH₂ O)_(n) CH₂ CH₂--, y has a value betwen 0.01 and x is a value from between zero andtwo.
 8. The composition of claim 7 wherein M is magnsium, n is 6.4, m is2, R⁴ is methyl, R³ is butyl and R² is hydrogen.
 9. The composition ofclaim 3 wherein M is magnesium, n is 2, R⁴ is ethyl, R³ is butyl, R² ishydrogen, R¹ is C₄ H₉ O--CH₂ CH₂ O--₂ CH₂ CH₂ -- and x is 0.5.
 10. Thecomposition of claim 3 wherein M is magnesium, n is 6.4, R³ is methyl,R⁴ is ethyl R² is hydrogen, R¹ is C₄ C₉ O--CH₂ CH₂ O--₂ CH₂ CH₂ --, andx is 0.25.
 11. An alkylmetalalkoxide of the formula

    (R.sup.1).sub.y M.sup.a (OCH(R.sup.2)CH.sub.2 --OCH(R.sup.2)Ch.sub.2).sub.n OR.sup.3).sub.a-y

wherein M^(a) is selected from magnesium, zinc, aluminum and mixturesthereof, a is the valence of M^(a), R¹ and R³ are independently selectedfrom C₁ to C₁₈ alkyl groups, R² is selected from hydrogen and methyl, nis a value from 1 to 20 and y is a value between 0.01 and 1.0.
 12. Analkymetalalkoxide of claim 11 wherein M^(a) is zinc, R¹ and R³ areindependently selected from C₁ to C₆ hydrocarbyl groups, R² is hydrogenand y is a value between 0.01 and 1.0.
 13. The alkylmetalalkoxide ofclaim 12 wherein R¹ is ethyl, R³ is methyl and n is 6.4.
 14. Thecomposition of claim 7 wherein M is magnesium, R² is hydrogen, R³ is aC₄ alkyl group, R⁴ is a C₄ alkyl group, n is equal to 2 and m is equalto
 2. 15. An alkalimetalkoxide of claim 11 wherein M^(a) is magnesium,R' and R³ are independently selected from C₁ -C₆ hydrocarbyl groups andR² is hydrogen.